Fluorinated organosilicon compounds



United States Patent FLUORINATED ORGANOSILICON COMPOUNDS Loren A. Haluska, Midland, Mich., assignor to Dow Corning Corporation, Midland, Mich, a corporation of Michigan No Drawing. Filed June 16, 1965, Ser. No. 464,552

Int. Cl. C07f 7/02, 7/04 US. Cl. 260-4482 4 Claims ABSTRACT OF THE DISCLOSURE There is provided by the invention an organosilicon compound of the formula where This application relates to new organsilicon compounds which are useful as water and oil repellents, protective coatings and lubricants.

The new compounds of this invention comprise at least one unit of the formula where R is selected from the group consisting of monovalent hydrocarbon and halohydrocarbon radicals, divalent hydrocarbon and halohydrocarbon radicals having both valences bonded to silicon atoms, the hydroxyl group, hydrogen, and hydrolyzable groups,

R is selected from the group consisting of methylene,

ethylene, propylene, and arylene radicals,

m has an average value of 1 to 20, and

n has an average value of from 0 to 3.

R can be any monovalent hydrocarbon radical, e.g. alkyl and cycloalkyl radicals such as methyl, isopropyl, sec-hexyl, octyl, octadecyl, and cyclohexyl; aliphatically unsaturated radicals such as vinyl, ethynyl, allyl, cyclopentenyl, and 3-octenyl; and aryl-containing radicals such as phenyl, tolyl, benzyl, Xenyl, or naphthyl.

R can also be any monovalent halohydrocarbon radical such as 3,3,3-trifluoropropyl, 4,5-dichloroootyl, bromocyclohexenyl, 3-ch1oroallyl, dibromophenyl, a,oc,oc-tllflll0- tolyl, and fluoroxenyl.

3,458,554 Patented July 29, 1969 p CC R can further be any divalent hydrocarbon or halohydrocarbon radicals, e.g. methylene, dimethylene,

phenylene, CH2OHZOHCH2CH2-,

Och and CHzCHCHg 31 3 Both valences are bonded to silicon atoms, for example ESiCI-I CH SiE.

R can also be any hydrolyzable group, i.e., any siliconbonded radical that reacts with water to form a silanol group. Examples are halogens such as chlorine and bromine; alkoxy groups such as methoxy, ethoxy, p-chloroethoxy, isopropoxy, and hexoxy; alkoxyallcoxy groups such as ,B-ethoxyethoxy, fl-methoxyethoxy, and B-methoxypropoxy; acyloxy groups such as formate, acetate, trifluoroacetate, and butyrate; a ketoxime derivative such as C2H5 C 112 0 H C5115 /CNO, /CNO, CNO, and (CHa)2ONO-- CH3 C H CH amino groups such as NH methylamino, dimethylamino, and oxyamino radicals such as ON(CH etc., and the isocyanate radical.

R can be any methylene, ethylene, propylene, or arylene radical such as phenylene, xenylene, or

In addition, this application relates to an organosilicon compound consisting essentially of at least one unit of the formula O H O SiR'O C (CmFzm) i ORSliO any other units present being of the formula nxsio where R is selected from the group consisting of monovalent hydrocarbon and halohydrocarbon radicals, divalent hydrocarbon and halohydrocarbon radicals having both valences bonded to silicon atoms, the hydroxyl group, hydrogen, and hydrolyzable groups,

R is selected from the group consisting of methylene,

ethylene, propylene, and arylene radicals,

m has an average value of l to 20,

n has an average value of from 0 to 3 and x has an average value of O to 3.

Examples of R and R are listed above. The compositions of this invention can be monomers such as:

CH2 CH2 CF: OF:

O nsrOOodmmiioOOsrn 0 0 II II (C4FQCHZCHzDQSiOOUC F CO siucuzou 2041*?) 1 in 311 They can also be homopolymers such as CH3 CH3 H OS iOH O( J o,Fm( iooH2s i)o1I and copolymers such as a SiO [SiOA/z] 0 5H3 2 ((1') 041102 4 S S I i Or/zSiCHzO O4F3CO CHzSiOr/g Ha H3 4 and o ESiR'OyXCmFzQ OR'SiE NaX This reaction proceeds well at temperatures around 100 C. It is often desirable to run the reaction in a suitable dispersing agent such as N,N-dimethylformamide, dibutylether, diethylketone, dimethylsulfoxide, or toluene.

Another. method of preparing the compositions of this invention is illustrated by Example 1 below.

A third method involves the addition of bisunsaturated esters such as the diallyl or divinyl esters of perfluorodicarboxylic acids, with ESlH compounds in the presence of addition catalysts such as chloroplatinic acid. This method is illustrated in Example 3.

The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.

4 Example 1 To 31.2 g. of perfiuorosuccinic acid there was added 36.1 g. of

o 0113 l (CH3 OCHzbOzO and 0.2 g. of sulfuric acid. This mixture was heated at 86 to 91 C. under a vacuum for 253 hours to yield a viscous polymer of the unit formula CH3 CH3 (I? (--OCHzSiO-SiCH2OC(GF2)3 CH3 H3 The viscosity of the polymer at 25 C. was 297.5 es, and the refractive index at 25 C. was 1.4111.

Example 2 When 10 g. of

is reacted with 1 g. of p-bromophenyldiphenylacetoxysilane at 100 C. in 20 g. of ethyleneglycoldirnethylether, a product is formed which is hydrolyzable to yield a polymer of the unit formula Example 3 When 10 g. of the diallyl ester of HOOC(C-;F COOH is reacted at C. with 2 g. of 3,3,3-trifluoropropylmethylchlorosilane in the presence of chloroplatinic acid, the product 1 i1 11 i ClSi(CH2)3OC(C F14)CO(GII2)aSiCl Hz Hg CH2 H2 is formed.

When equimolar amounts of the above product and CH3 CH3 l CH3 CH3 are mixed, a polymer consisting essentially of CH 0 0 CH CH OH;

I ll [5 I SI(CH2)3OC(C1F14 ()(CHz)3SlO-;Sl S10- 5H3 (5H2 CH3 H; i 1 OF: C a

units is formed.

That which is claimed is: 1. An organosilicon compound of the unit formula where R is selected from the group consisting of monovalent hydrocarbon and halohydrocarbon radicals, divalent hydrocarbon and halohydrocarbon radicals havthe remaining units present being of the formula where R is selected from the group consisting of monovalent hydrocarbon and halohydrocarbon radicals, divalent hydrocarbon and halohydrocarbon radicals having both valences bonded to silicon atoms, the hydroxyl group, hydrogen, and hydrolyzable groups,

R is selected from the group consisting of methylene,

ethylene, propylene, and arylene radicals,

m has an average value of 1 to 20,

n has an average value of from 0 to 3 and x has an average value of O to 3.

3. A compound in accordance with claim 1 where R is methyl, R is methylene, m has a value of 1 and n has a value of 2.

4. A compound in accordance with claim 2 where R is methyl, R is methylene, m has a value of 1 and n has a value of 2.

References Cited UNITED STATES PATENTS 3,347,794 10/ 1967 Kawahara 260-448.2 XR 3,371,104 2/1968 Rossmy et a1. 260-4482. XR 3,161,664 12/1964 Depree 260429.7 XR 3,249,464 5/1966 Nelson et al. 11776 XR TOBIAS E. LEVOW, Primary Examiner J. P. PODGORSKI, Assistant Examiner U.S. Cl. X.R. 

